Interaction of <i>N</i>‐Heterocyclic Carbenes and Simple Carbenes with Small Molecules (One to Three Atoms) Excluding Metals: Formation of Covalent C–X Bonds

Alkorta, Ibón; Elguero, José

doi:10.1002/jhet.3331

Cited by 10 publications

(2 citation statements)

References 154 publications

(175 reference statements)

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“…The tautomerism of these small molecules has been studied theoretically many times with an increasing level of theoretical calculations. The values in kJ·mol –1 (method) with regard to the most stable one, 1 H ‐1,2,4‐triazole, 3a , are in chronological order: 20.9 (INDO), 25 28.0 (RHF/6‐31G[d]//RHF/6‐31G), 26 26.3 (RHF/6‐31G(d,p)//RHF/3‐21G) + ZPE + MP2], 27 30.1 [MP2/6‐31G(d)//RHF/6‐31G(d)], 28 36.0 (MINDO/3), 29 29.8 [Becke3P86/6‐311G(d,p)], 29 28.9 [RHF/6‐311G(d,p)], 30 28.8 [B3LYP/6‐31G(d)], 31 26.7 [MP2‐(fc)/6‐311 + G(d,p)], 32 28.5 [B3LYP/6‐311++G(d,p)], 33 30.1 [B3PW91/6‐311++G(d,p)], and 26.0 [B3LYP/6‐311++g(d,p)], 34 26.0 (CBS‐4 M), 35 24.9 (CBS‐QB3) 35 and 26.1 CCSD(T)/cc‐pCVTZ 35 …”

Section: Resultsmentioning

confidence: 99%

Addition reaction of azoles to acetone‐d₆: NMR and computational studies

Claramunt,

Sanz,

Alkorta

et al. 2024

J of Physical Organic Chem

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The reactivity of imidazole, pyrazole, 1,2,4‐triazole, 1,2,3‐triazole, and tetrazole with acetone (propan‐2‐one) has been studied by 1H and 13C NMR using acetone‐d6 as solvent at temperatures ranging from 173 to 300 K at 10 K intervals. Simultaneously, the reaction has been theoretically calculated at the B3LYP/6‐311++G(d,p) level, and experimental and theoretical results have been compared. The equilibrium constants between azoles and adducts α,α‐dimethyl‐azole‐methanol were analyzed, assuming that the straight part of the plots –R ln Ke vs. 1/T can be used to determine ΔH and ΔS. Calculated and experimental data are related, but the theoretical values are proportionally higher. The tautomerism of triazoles and tetrazole has been considered in order to discuss the reactions.

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Section: Resultsmentioning

confidence: 99%

Addition reaction of azoles to acetone‐d₆: NMR and computational studies

Claramunt,

Sanz,

Alkorta

et al. 2024

J of Physical Organic Chem

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“…Other 1,3-dipolar cycloadditions in which CO 2 is the dipolarophile ( 3a → 3b ) , have formal relationships such as described above. There are other systems such as carbenes, − phosphines, and guanidines that can react with CO 2 to form such adducts.…”

Section: Introductionmentioning

confidence: 99%

Potential Energy Surfaces of HN(CH)SX:CO₂for X = F, Cl, NC, CN, CCH, and H: N···C Tetrel Bonds and O···S Chalcogen Bonds

2019

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MP2/aug′-cc-pVTZ calculations have been performed in search of complexes, molecules, and transition structures on the HN(CH)SX:CO2 potential energy surfaces, for X = F, Cl, NC, CN, CCH, and H. Complexes stabilized by traditional N···C tetrel bonds and O···S chalcogen bonds exist on all surfaces and are bound relative to the isolated monomers. Molecules stabilized by an N–C covalent bond and an O···S chalcogen bond are found when X = F, Cl, and NC, but only the HN(CH)SF:CO2 molecule is bound. The binding energies of these complexes correlate with the O–S distance but not with the N–C distance. Binding energies of complexes rotated by 90° about the N···C tetrel bond and by 90° about the O···S chalcogen bond provide estimates of these bond energies. Charge-transfer energies across tetrel and chalcogen bonds correlate with the N–C and O–S distances, respectively. As a function of the N–C distance, equation-of-motion coupled cluster singles and doubles spin–spin coupling constants 1t J(N–C) for complexes and transition structures and 1 J(N–C) for molecules describe the evolution of the N···C tetrel bonds in the complexes and transition structures to N–C covalent bonds in the molecules. The O···S chalcogen bond gains some covalency in the transition structures and again in the molecules but does not become a covalent bond.

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Ferrocene‐Based N‐Heterocyclic Plumbylenes [Fe{(η⁵‐C₅H₄)NSiMe₂R}₂Pb:]: Influence of the Steric Demand of theN‐Substituents on Their Dimerization via C−H Activation with Pb^II

Guthardt,

Jacob,

Herle

et al. 2023

Chemistry An Asian Journal

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Ferrocene‐based N‐heterocyclic plumbylenes fc[(NSiMe2R)2Pb:] (1; fc=1,1’‐ferrocenylene) are easily accessible by transamination from [(Me3Si)2N]2Pb and the corresponding 1,1’‐diaminoferrocene derivatives fc(NHSiMe2R)2. They may form unconventional dimers 2 by a process, which causes the cleavage of a cyclopentadienyl C−H bond and the formation of a Pb−C and an N−H bond. The monomer‐dimer equilibrium (2 1⇆2) has been addressed experimentally and computationally. It critically depends on the steric demand of the N‐substituents SiMe2R, which has been varied systematically by using homologues with aliphatic (R=methyl, ethyl, isopropyl, tert‐butyl) and aromatic units (R=phenyl, mesityl, ferrocenyl). Even in the sterically least congested case (R=methyl), dimerization is only slightly exergonic. It eventually becomes prohibitively endergonic with increasingly larger substituents and is thus not observed for R=tert‐butyl, mesityl, and ferrocenyl. R=phenyl represents a borderline case, where the dimer is still detectable in the equilibrium mixture, albeit as a very minor component, in accord with the slightly endergonic Gibbs free energy change calculated for its formation. Addition of 4‐dimethylaminopyridine (DMAP) to the monomer‐dimer equilibrium mixtures cleanly affords the corresponding adducts [1(DMAP)], irrespective of the equilibrium composition.

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Interaction of N‐Heterocyclic Carbenes and Simple Carbenes with Small Molecules (One to Three Atoms) Excluding Metals: Formation of Covalent C–X Bonds

Cited by 10 publications

References 154 publications

Addition reaction of azoles to acetone‐d₆: NMR and computational studies

Addition reaction of azoles to acetone‐d₆: NMR and computational studies

Potential Energy Surfaces of HN(CH)SX:CO₂for X = F, Cl, NC, CN, CCH, and H: N···C Tetrel Bonds and O···S Chalcogen Bonds

Ferrocene‐Based N‐Heterocyclic Plumbylenes [Fe{(η⁵‐C₅H₄)NSiMe₂R}₂Pb:]: Influence of the Steric Demand of theN‐Substituents on Their Dimerization via C−H Activation with Pb^II

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Interaction of N‐Heterocyclic Carbenes and Simple Carbenes with Small Molecules (One to Three Atoms) Excluding Metals: Formation of Covalent C–X Bonds

Cited by 10 publications

References 154 publications

Addition reaction of azoles to acetone‐d6: NMR and computational studies

Addition reaction of azoles to acetone‐d6: NMR and computational studies

Potential Energy Surfaces of HN(CH)SX:CO2for X = F, Cl, NC, CN, CCH, and H: N···C Tetrel Bonds and O···S Chalcogen Bonds

Ferrocene‐Based N‐Heterocyclic Plumbylenes [Fe{(η5‐C5H4)NSiMe2R}2Pb:]: Influence of the Steric Demand of theN‐Substituents on Their Dimerization via C−H Activation with PbII

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Addition reaction of azoles to acetone‐d₆: NMR and computational studies

Addition reaction of azoles to acetone‐d₆: NMR and computational studies

Potential Energy Surfaces of HN(CH)SX:CO₂for X = F, Cl, NC, CN, CCH, and H: N···C Tetrel Bonds and O···S Chalcogen Bonds

Ferrocene‐Based N‐Heterocyclic Plumbylenes [Fe{(η⁵‐C₅H₄)NSiMe₂R}₂Pb:]: Influence of the Steric Demand of theN‐Substituents on Their Dimerization via C−H Activation with Pb^II